CN105332081A - Preparing method for ablation-resistant high-ortho phenolic fibers - Google Patents

Preparing method for ablation-resistant high-ortho phenolic fibers Download PDF

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CN105332081A
CN105332081A CN201510781949.4A CN201510781949A CN105332081A CN 105332081 A CN105332081 A CN 105332081A CN 201510781949 A CN201510781949 A CN 201510781949A CN 105332081 A CN105332081 A CN 105332081A
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fibre
temperature
ortho position
boronphenolic
ablation
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CN105332081B (en
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杨凯
焦明立
刁泉
曹健
宋慧娟
陈燕
米立伟
朱方龙
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Zhongyuan University of Technology
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Zhongyuan University of Technology
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Abstract

The invention discloses a preparing method for ablation-resistant high-ortho phenolic fibers. A phenolic compound and formaldehyde are mixed according to a certain proportion, then a certain amount of citric acid as a catalyst is added, and a boiling reaction is carried out for 0.5-4 h; diluted concentrated sulfuric acid is added, and the reaction continues for 30-50 min; decompression and dehydration are carried out for 0.5-2.9 h, boric acid accounting for 1-8% by mass is added for a modification reaction after the temperature reaches 90-97 DEG C, and boiling is carried out for 2 h at the constant temperature; decompression and dehydration are carried out, and dehydration is stopped when the temperature of resin reaches 110 DEG C; the resin is subjected to melt spinning at 120-160 DEG C; nascent fibers are put into a prepared curing solution, the temperature is increased to 95 DEG C gradually from the room temperature, and the nascent fibers are naturally cooled to the room temperature after constant temperature is achieved; the temperature is gradually increased for thermosetting under the nitrogen condition. The fiber strength of the high-ortho phenolic fibers ranges from 3 cN/dtex to 36 cN/dtex, the modulus ranges from 40 cN/dtex to 400 cN/dtex, and the cross-linking degree ranges from 32% to 38%.

Description

The preparation method of a kind of height of resistance to ablation ortho position boronphenolic fibre
Technical field
The invention belongs to the preparation field of the extraordinary fiber of resistance to ablation, particularly the preparation method of a kind of height of resistance to ablation ortho position boronphenolic fibre.
Background technology
Common phenolic aldehyde can below 150 DEG C Long-Time Service, but exceed this temperature obvious oxidative phenomena just occur.And along with the rising of temperature, there is pyrolysis, carbonization phenomenon in phenolic aldehyde successively.For improving the heat resistance of phenolic fibre, chemical method is usually adopted to carry out modification to resin, as [Wang Hongbin, the Dang Jiangmin such as phenolic hydroxyl group etherificate, esterification, heavy metal chelating by phenolic fibre, Ren Rui etc., synthetic fiber industry, 2012,35 (2), 12-15, USPat4851279].Improve the heat resistance of common phenolic aldehyde by these methods, extend the scope of application of phenolic fibre.Also can utilize the electrophilic performance of B-O base simultaneously, improve the electron rich state on phenyl ring, reduce the activity of methylene on phenolic fibre, improve the heat endurance of phenolic aldehyde.In phenolic aldehyde, introduce boron element makes traditional thermosetting phenolic resin various aspects of performance be improved [CN102443181B] to its modification, achieves good effect.
Boron modified phenolic resin has more superior resistance to ablation, heat resistance, instantaneous heat-resisting quantity and mechanical property than traditional phenol-formaldehyde resin modified, mainly concentrate on the fields of space technology such as rocket, guided missile, spacecraft as excellent ablation resistant material, automobile brake sheet etc.But boron modification phenolic aldehyde has no application in fibre modification, also have no report in the modification of high ortho phenolic fiber.Simultaneously due to the restriction of phenolic resins chemical constitution, the improvement of thermoplastic phenolic fibre property mostly improves on single performance, and declining appears in other performances, is difficult to the multinomial performance significantly improving phenolic fibre on the original basis.
Summary of the invention
For solving above-mentioned prior art Problems existing, the object of the present invention is to provide the preparation method of a kind of height of resistance to ablation ortho position boronphenolic fibre.
There is spinning properties difference for phenolic fibre in prior art, the co-blended spinnings such as normal needs and PVA or PA, the fibrous mechanical property obtained is poor, and heat resistance is not enough, and ablation resistance is short of, and is difficult to prolonged application at special dimension.The present invention proposes and synthesize high ortho position boron bakelite resin by gentle method, and spinning, obtain ablation resistance excellence by two-stage cure, the high ortho position boronphenolic fibre that resistance to elevated temperatures, mechanical property greatly improve.
For achieving the above object, technical scheme of the present invention is:
A preparation method for the height of resistance to ablation ortho position boronphenolic fibre, comprises the steps:
(1) mixed phenols compound and formaldehyde according to a certain percentage, adds a certain amount of catalyst Titanium Citrate, boiling reaction 0.5 ~ 2.9h afterwards; Above-mentioned phenolic compound is any one in phenol, paracresol, xylenol;
(2) add diluting concentrated sulfuric acid, continue reaction 30min ~ 50min;
(3) decompression dehydration 0.5-3h, resin temperature arrives 90-97 DEG C;
(4) adding mass ratio is that the boric acid of phenolic compound amount 1-10% carries out modified-reaction, and constant temperature seethes with excitement 2 hours;
(5) decompression dehydration, until resin temperature rises to 100-130 DEG C of discharging, to obtain molecular weight be 5000-30000Da, O/P(adjacency pair position than) value is 4-8,140 DEG C of viscosity are the high ortho position boric acid phenolic resins of 9-30.5cP;
(6) by resin at 120-160 DEG C of melt spinning;
(7) as-spun fibre is put into the consolidation liquid configured, from room temperature, be progressively warming up to 95 DEG C, constant temperature 0-2 hour, then naturally cools to room temperature;
Filament after one step solidification takes out and cleans and dry by (8) two step solidifications, and put into vacuum drying oven afterwards, set temperature is 50 DEG C and vacuumizes 2 hours, pass into nitrogen, progressively be warming up to 240 DEG C, keep naturally cooling to room temperature after 0-2 hour, obtain high ortho position boronphenolic fibre.
Further, in described step one, the mol ratio of phenolic compound and formaldehyde is 1:0.8-0.9, and phenolic compound and Titanium Citrate mass ratio are 100:1-3, react and carry out in there-necked flask.
Further, in described step 2, every 100g phenolic compound adds the 0.1-0.4ml concentrated sulfuric acid.
Further, in described step 7, consolidation liquid adopts formaldehyde mass fraction 18 ﹪, the aqueous solution of hydrochloric acid mass fraction 12%.
Further, in described step 7, the heating rate from room temperature is: within every 2 minutes, rise 1-6 DEG C.
Further, in described step 8, the heating rate being warming up to 240 DEG C is: within every 2 minutes, rise 5-20 DEG C.
Relative to prior art, beneficial effect of the present invention is: the present invention compared with prior art selects Titanium Citrate as catalyst, boron modification, there is reaction rate fast, simple, resin adjacency pair position is higher than (O/P) value, melt is even, viscosity is low, spinning is easy under high molecular condition, spinning properties is good, solidification rate is fast, the degree of cross linking is high, by increasing B-O key in the phenolic aldehyde molecule of high ortho position, because B-O is positioned on main chain, add the energy to failure of phenolic aldehyde molecule, improve compliance, thus make the ablation resistance of high ortho position boronphenolic fibre, heat endurance, mechanical property and anti-flammability are obtained for raising, improve the heat endurance of fiber on the one hand, anti-flammability and ablation resistance, solve high ortho phenolic fiber fragility on the other hand large, the shortcoming that intensity is lower, obtain the high ortho position boronphenolic fibre of excellent combination property.
The fibre strength of high ortho position boronphenolic fibre is 3-36cN/dtex, modulus is 40-400cN/dtex, degree of cross linking 32-38%, heat decomposition temperature reaches about 420 DEG C, carbon left under 1000 DEG C of nitrogen atmospheres is up to 60-79%, limited oxygen index is 34-43, thus obtains mechanical property, ablation resistance excellence, the high ortho position boronphenolic fibre that heat resistance, anti-flammability improve.
Accompanying drawing explanation
Fig. 1 is the hot property of the high ortho position boron phenolic aldehyde two step cured fiber of 8% boric acid content.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, technical solution of the present invention is described in further detail:
Embodiment 1
According to mixed in molar ratio phenol (100g) and the formaldehyde (68.9g) of 1:0.8, add 1g Titanium Citrate catalyst afterwards, boiling reaction 2.9h; Add diluting concentrated sulfuric acid (concentrated sulfuric acid is 0.1ml), continue reaction 50min; Decompression dehydration 0.5h, resin temperature arrives 90 DEG C; Adding quality is that the boric acid of 1g carries out modified-reaction, and constant temperature seethes with excitement 2 hours; Decompression dehydration, when resin temperature rises to 100 DEG C of dischargings, to obtain molecular weight be 26000Da, O/P(adjacency pair position than) the high ortho position boric acid phenolic resins of value to be 4.5,140 DEG C of viscosity be 24.5cP;
Resin is at 120 DEG C of melt spinnings, put into by as-spun fibre in the consolidation liquid (formaldehyde mass fraction 8 ﹪, the aqueous solution of hydrochloric acid mass fraction 12%) configured, progressively heat up from room temperature (within every 2 minutes, rising 1 DEG C) rises to 95 DEG C, constant temperature 0 hour, then naturally cools to room temperature;
To clean after silk after one step solidification is taken out and after drying, put into vacuum drying oven, set temperature is 50 DEG C and vacuumizes 2 hours, pass into nitrogen, progressively heat up (within every 2 minutes, rising 5 DEG C) to 240 DEG C, keep naturally cooling to room temperature after 0 hour, obtain high ortho position boronphenolic fibre.
The fibre strength of 6% high ortho position boronphenolic fibre is 4cN/dtex, and modulus is 40cN/dtex, the degree of cross linking 33%, and heat decomposition temperature reaches 290 DEG C, and the carbon left under 1000 DEG C of nitrogen atmospheres is 62%, and limited oxygen index is 36.
Embodiment 2
According to mixed in molar ratio phenol (100g) and the formaldehyde (73.3g) of 1:0.85, add 2g Titanium Citrate catalyst afterwards, boiling reaction 2h; Add diluting concentrated sulfuric acid (concentrated sulfuric acid is 0.3ml), continue reaction 30min; Decompression dehydration 3h, resin temperature arrives 97 DEG C; Adding quality is that the boric acid of 10g carries out modified-reaction, and constant temperature seethes with excitement 2 hours; Decompression dehydration, when resin temperature rises to 130 DEG C of dischargings, to obtain molecular weight be 5000Da, O/P(adjacency pair position than) the high ortho position boric acid phenolic resins of value to be 7.8,140 DEG C of viscosity be 9.5cP;
Resin is at 160 DEG C of melt spinnings, put into by as-spun fibre in the consolidation liquid (formaldehyde mass fraction 6 ﹪, the aqueous solution of hydrochloric acid mass fraction 12%) configured, progressively heat up from room temperature (within every 2 minutes, rising 6 DEG C) rises to 95 DEG C, constant temperature 2 hours, then naturally cools to room temperature;
To clean after silk after one step solidification is taken out and after drying, put into vacuum drying oven, set temperature is 50 DEG C and vacuumizes 2 hours, pass into nitrogen, progressively heat up (within every 2 minutes, rising 20 DEG C) to 240 DEG C, keep naturally cooling to room temperature after 2 hours, obtain high ortho position boronphenolic fibre.
The fibre strength of 10% high ortho position boronphenolic fibre is 32cN/dtex, and modulus is 380cN/dtex, the degree of cross linking 38%, and heat decomposition temperature reaches 350 DEG C, and the carbon left under 1000 DEG C of nitrogen atmospheres is 70%, and limited oxygen index is 42.Be illustrated in figure 1 the hot property of 10% high ortho position boron phenolic aldehyde two step cured fiber.
Embodiment 3
The high ortho position boronphenolic fibre of embodiment 2 gained and phenolic resins carry out compound according to the mass ratio of 4:6 and obtain high ortho position boronphenolic fibre/phenolic resin composite, this heat conductivity is 0.39W/m*K, linear ablative rate is-0.010mm/s, oxy-acetylene flame mass ablative rate is 0.0213g/s, and density is 1.31g/cm 3, the carbon left under 1000 DEG C of nitrogen atmospheres is 75%, and limited oxygen index is 40.It is good that result shows that this composite material interface combines, and ablation resistance is excellent, and improve than thermal insulation, heat resistance and anti-flammability with phenolic resins, cooperative effect is obvious.
Embodiment 4
The fiber of embodiment 2 gained is made into 140g/m 2, the plain cloth of thickness 0.31mm, limited oxygen index is carbonize in nitrogen after 43,280 DEG C of oxidations, and 850 DEG C of steam activations, obtain specific area 2280m 2the active carbon fibre fabric of/g, aperture 3.1nm, extension at break 3.9%, iodine absorption number is 2600mg/g.
Embodiment 5
According to mixed in molar ratio phenol (100g) and the formaldehyde (77.6g) of 1:0.9, add 3g Titanium Citrate catalyst afterwards, boiling reaction 0.5h; Add diluting concentrated sulfuric acid (concentrated sulfuric acid is 0.4ml), continue reaction 40min; Decompression dehydration 2h, resin temperature arrives 95 DEG C; Adding quality is that the boric acid of 5g carries out modified-reaction, and constant temperature seethes with excitement 2 hours; Decompression dehydration, when resin temperature rises to 120 DEG C of dischargings, to obtain molecular weight be 27000Da, O/P(adjacency pair position than) the high ortho position boric acid phenolic resins of value to be 6.7,140 DEG C of viscosity be 20cP;
Resin is at 150 DEG C of melt spinnings, put into by as-spun fibre in the consolidation liquid (formaldehyde mass fraction 18 ﹪, the aqueous solution of hydrochloric acid mass fraction 12%) configured, progressively heat up from room temperature (within every 2 minutes, rising 4 DEG C) rises to 95 DEG C, constant temperature 1 hour, then naturally cools to room temperature;
To clean after silk after one step solidification is taken out and after drying, put into vacuum drying oven, set temperature is 50 DEG C and vacuumizes 2 hours, pass into nitrogen, progressively heat up (within every 2 minutes, rising 12 DEG C) to 240 DEG C, keep naturally cooling to room temperature after 1 hour, obtain high ortho position boronphenolic fibre.
The fibre strength of 5% high ortho position boronphenolic fibre is 28cN/dtex, and modulus is 200cN/dtex, the degree of cross linking 36%, and heat decomposition temperature reaches 420 DEG C, and the carbon left under 1000 DEG C of nitrogen atmospheres is 78%, and limited oxygen index is 43.
Embodiment 6
According to mixed in molar ratio paracresol (100g) and the formaldehyde (67.5g) of 1:0.9, add 2.5g Titanium Citrate catalyst afterwards, boiling reaction 1.5h; Add diluting concentrated sulfuric acid (concentrated sulfuric acid is 0.2ml), continue reaction 45min; Decompression dehydration 2h, resin temperature arrives 94 DEG C; Adding quality is that the boric acid of 3g carries out modified-reaction, and constant temperature seethes with excitement 2 hours; Decompression dehydration, when resin temperature rises to 125 DEG C of dischargings, to obtain molecular weight be 28000Da, O/P(adjacency pair position than) the high ortho position boric acid phenolic resins of value to be 4.7,140 DEG C of viscosity be 23cP;
Resin is at 145 DEG C of melt spinnings, put into by as-spun fibre in the consolidation liquid (formaldehyde mass fraction 18 ﹪, the aqueous solution of hydrochloric acid mass fraction 12%) configured, progressively heat up from room temperature (within every 2 minutes, rising 3 DEG C) rises to 95 DEG C, constant temperature 0.9 hour, then naturally cools to room temperature;
To clean after silk after one step solidification is taken out and after drying, put into vacuum drying oven, set temperature is 50 DEG C and vacuumizes 2 hours, pass into nitrogen, progressively heat up (within every 2 minutes, rising 10 DEG C) to 240 DEG C, keep naturally cooling to room temperature after 1.5 hours, obtain high ortho position boronphenolic fibre.
The fibre strength of 3% high ortho position boronphenolic fibre is 24cN/dtex, and modulus is 30cN/dtex, the degree of cross linking 34%, and heat decomposition temperature reaches 420 DEG C, and the carbon left under 1000 DEG C of nitrogen atmospheres is 78%, and limited oxygen index is 41.
Embodiment 7
According to mixed in molar ratio xylenol (100g) and the formaldehyde (66.4g) of 1:0.85, add 2.1g Titanium Citrate catalyst afterwards, boiling reaction 0.8h; Add diluting concentrated sulfuric acid (concentrated sulfuric acid is 0.3ml), continue reaction 44min; Decompression dehydration 2h, resin temperature arrives 95 DEG C; Adding quality is that the boric acid of 5g carries out modified-reaction, and constant temperature seethes with excitement 2 hours; Decompression dehydration, when resin temperature rises to 130 DEG C of dischargings, to obtain molecular weight be 28000Da, O/P(adjacency pair position than) the high ortho position boric acid phenolic resins of value to be 5.7,140 DEG C of viscosity be 20cP;
Resin is at 150 DEG C of melt spinnings, put into by as-spun fibre in the consolidation liquid (formaldehyde mass fraction 18 ﹪, the aqueous solution of hydrochloric acid mass fraction 12%) configured, progressively heat up from room temperature (within every 2 minutes, rising 5 DEG C) rises to 95 DEG C, constant temperature 1 hour, then naturally cools to room temperature;
To clean after silk after one step solidification is taken out and after drying, put into vacuum drying oven, set temperature is 50 DEG C and vacuumizes 2 hours, pass into nitrogen, progressively heat up (within every 2 minutes, rising 15 DEG C) to 240 DEG C, keep naturally cooling to room temperature after 1 hour, obtain high ortho position boronphenolic fibre.
The fibre strength of 5% high ortho position boronphenolic fibre is 25cN/dtex, and modulus is 56cN/dtex, the degree of cross linking 36%, and heat decomposition temperature reaches 414 DEG C, and the carbon left under 1000 DEG C of nitrogen atmospheres is 74%, and limited oxygen index is 43.

Claims (4)

1. a preparation method for the height of resistance to ablation ortho position boronphenolic fibre, is characterized in that its step is as follows:
(1) phenolic compound is mixed with formaldehyde, then Titanium Citrate is added, boiling reaction 0.5 ~ 2.9h, described phenolic compound is any one in phenol, paracresol, xylenol, described phenolic compound is 1:0.8-0.9 with the ratio of the amount of substance of formaldehyde, and the mass ratio of phenolic compound and Titanium Citrate is 100:1-3;
(2) add the concentrated sulfuric acid, every 100g phenolic compound adds the 0.1-0.4ml concentrated sulfuric acid, continues reaction 30min ~ 50min;
(3) decompression dehydration 0.5-3h, resin temperature arrives 90-97 DEG C;
(4) add boric acid, described boric acid add the 1-10% that quality is phenolic compound quality, constant temperature seethes with excitement 2 hours;
(5) decompression dehydration, until resin temperature rises to 100-130 DEG C of discharging, obtains high ortho position boric acid phenolic resins;
(6) by high ortho position boric acid phenolic resins melt spinning under 120-160 DEG C of condition, as-spun fibre is obtained;
(7) as-spun fibre is put into the consolidation liquid configured, from room temperature, be progressively warming up to 95 DEG C, constant temperature 0-2 hour, then naturally cools to room temperature, obtains filament;
(8) filament taking-up is cleaned and dried, put into vacuum drying oven afterwards, set temperature is 50 DEG C and vacuumizes 2 hours, passes into nitrogen, is progressively warming up to 240 DEG C, keeps naturally cooling to room temperature after 0-2 hour, obtains high ortho position boronphenolic fibre.
2. the preparation method of the height of resistance to ablation ortho position according to claim 1 boronphenolic fibre, is characterized in that: in described step (7) consolidation liquid to be mass fraction be 18% formaldehyde and mass fraction be the mixed liquor of the hydrochloric acid of 12%.
3. the preparation method of the height of resistance to ablation ortho position according to claim 1 boronphenolic fibre, is characterized in that: in described step (7), heating rate is rise 1-6 DEG C in every 2 minutes.
4. the preparation method of the height of resistance to ablation ortho position according to claim 1 boronphenolic fibre, is characterized in that: in described step (8), heating rate is rise 5-20 DEG C in every 2 minutes.
CN201510781949.4A 2015-11-16 2015-11-16 A kind of preparation method of the high ortho position boronphenolic fibre of resistance to ablation Expired - Fee Related CN105332081B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108823798A (en) * 2018-07-27 2018-11-16 中原工学院 A kind of preparation method of the modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base of molybdic acid phenyl ester
CN108950720A (en) * 2018-07-27 2018-12-07 中原工学院 A method of the modified high ortho phenolic fiber of phenyl-borate is prepared by wet spinning
CN109957208A (en) * 2019-03-28 2019-07-02 中国人民解放军国防科技大学 Light micro-ablation composite material and preparation method thereof

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US4778633A (en) * 1985-04-01 1988-10-18 Raychem Corporation Method of making high strength polyethylene fiber
CN101289768A (en) * 2008-06-13 2008-10-22 陕西师范大学 Method for preparing boronphenolic fibre
CN101289767A (en) * 2008-06-13 2008-10-22 陕西师范大学 Method for preparing phenolic resin fiber of high molecular weight
CN103289033A (en) * 2013-04-08 2013-09-11 西安交通大学 Aryl boron-containing phenolic resin and preparation method thereof

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US4778633A (en) * 1985-04-01 1988-10-18 Raychem Corporation Method of making high strength polyethylene fiber
CN101289768A (en) * 2008-06-13 2008-10-22 陕西师范大学 Method for preparing boronphenolic fibre
CN101289767A (en) * 2008-06-13 2008-10-22 陕西师范大学 Method for preparing phenolic resin fiber of high molecular weight
CN103289033A (en) * 2013-04-08 2013-09-11 西安交通大学 Aryl boron-containing phenolic resin and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108823798A (en) * 2018-07-27 2018-11-16 中原工学院 A kind of preparation method of the modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base of molybdic acid phenyl ester
CN108950720A (en) * 2018-07-27 2018-12-07 中原工学院 A method of the modified high ortho phenolic fiber of phenyl-borate is prepared by wet spinning
CN108823798B (en) * 2018-07-27 2020-08-07 中原工学院 Preparation method of phenyl molybdate modified high-ortho thermosetting phenolic-based hollow nano gradient activated carbon fiber membrane
CN109957208A (en) * 2019-03-28 2019-07-02 中国人民解放军国防科技大学 Light micro-ablation composite material and preparation method thereof
CN109957208B (en) * 2019-03-28 2021-11-05 中国人民解放军国防科技大学 Light micro-ablation composite material and preparation method thereof

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